Hierarchical self-assembly of chiral complementary hydrogen-bond networks in water: Reconstitution of supramolecular membranes

T. Kawasaki, M. Tokuhiro, Nobuo Kimizuka, Toyoki Kunitake

Research output: Contribution to journalArticle

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Abstract

Spontaneous formation of complementary hydrogen-bond pairs and their hierarchical self-assembly (reconstitution) into chiral supramolecular membranes are achieved in water by mixing amphiphilic pairs of glutamate-derived melamine 6 and ammonium-derivatized azobenzene cyanuric acid 4. Electron microscopy is used to observe formation of helical superstructures, which are distinct from the aggregate structures observed for each of the single components in water. In addition, a spectral blue-shift and induced circular dichroism (ICD) with exciton coupling are observed for the π-π* absorption of the azobenzene chromophores. These observations are consistent with the reconstitution of the hydrogen-bond-mediated supramolecular membrane 6-4. Spectral titration experiments indicate the stoichiometric integration of the complementary subunits with an association constant of 1.13 × 105 M-1. This value is considerably larger than those reported for the artificial hydrogen-bonding complexes in aqueous media. The remarkable reconstitution efficiency is ascribed to the hydrophobically driven self-organization of the amphiphilic, linear hydrogen-bond networks in water. Molecular structure of the complementary subunits plays an important role in the complexation process since it is restricted by the photoisomerized cis-azobenzene subunit. On the other hand, thermally regenerated trans-isomer 4 undergoes facile complexation with the counterpart 6. The present reconstitution of supramolecular membranes provides the first example of complementary hydrogen-bond-directed formation of soluble, mesoscopic supramolecular assemblies in water.

Original languageEnglish
Pages (from-to)6792-6800
Number of pages9
JournalJournal of the American Chemical Society
Volume123
Issue number28
DOIs
Publication statusPublished - Oct 2 2001

Fingerprint

Self assembly
Hydrogen
Hydrogen bonds
Azobenzene
Membranes
Water
Complexation
Pair Bond
Hydrogen Bonding
Circular Dichroism
Molecular Structure
Ammonium Compounds
Melamine
Dichroism
Glutamic Acid
Chromophores
Electron Microscopy
Titration
Excitons
Isomers

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Hierarchical self-assembly of chiral complementary hydrogen-bond networks in water : Reconstitution of supramolecular membranes. / Kawasaki, T.; Tokuhiro, M.; Kimizuka, Nobuo; Kunitake, Toyoki.

In: Journal of the American Chemical Society, Vol. 123, No. 28, 02.10.2001, p. 6792-6800.

Research output: Contribution to journalArticle

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